CN100502127C - Lithium ion secondary battery with large current discharge capability - Google Patents
Lithium ion secondary battery with large current discharge capability Download PDFInfo
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- CN100502127C CN100502127C CNB2006100026365A CN200610002636A CN100502127C CN 100502127 C CN100502127 C CN 100502127C CN B2006100026365 A CNB2006100026365 A CN B2006100026365A CN 200610002636 A CN200610002636 A CN 200610002636A CN 100502127 C CN100502127 C CN 100502127C
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- positive electrode
- rechargeable battery
- lithium rechargeable
- base material
- lithium
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- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 11
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 11
- 239000011248 coating agent Substances 0.000 claims abstract description 36
- 238000000576 coating method Methods 0.000 claims abstract description 36
- 239000007774 positive electrode material Substances 0.000 claims abstract description 30
- 229910010710 LiFePO Inorganic materials 0.000 claims abstract description 6
- 229910052744 lithium Inorganic materials 0.000 claims description 53
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 44
- 239000000463 material Substances 0.000 claims description 42
- 229910010707 LiFePO 4 Inorganic materials 0.000 claims description 24
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 10
- 229910052799 carbon Inorganic materials 0.000 claims description 10
- 229910052759 nickel Inorganic materials 0.000 claims description 8
- 229910012851 LiCoO 2 Inorganic materials 0.000 claims description 6
- 229910015645 LiMn Inorganic materials 0.000 claims description 6
- 150000002642 lithium compounds Chemical class 0.000 claims description 6
- 229910052723 transition metal Inorganic materials 0.000 claims description 6
- 229910052782 aluminium Inorganic materials 0.000 claims description 5
- 230000004888 barrier function Effects 0.000 claims description 5
- 239000003792 electrolyte Substances 0.000 claims description 5
- 150000002641 lithium Chemical class 0.000 claims description 5
- 239000002075 main ingredient Substances 0.000 claims description 5
- 229910052609 olivine Inorganic materials 0.000 claims description 5
- 239000010450 olivine Substances 0.000 claims description 5
- 229910013275 LiMPO Inorganic materials 0.000 claims description 4
- 239000000853 adhesive Substances 0.000 claims description 4
- 230000001070 adhesive effect Effects 0.000 claims description 4
- -1 lithium transition-metal phosphorus compound Chemical class 0.000 claims description 4
- 229910052748 manganese Inorganic materials 0.000 claims description 4
- 229910052698 phosphorus Inorganic materials 0.000 claims description 4
- 239000011574 phosphorus Substances 0.000 claims description 4
- 239000013078 crystal Substances 0.000 claims description 3
- 238000012986 modification Methods 0.000 claims description 2
- 230000004048 modification Effects 0.000 claims description 2
- 150000003624 transition metals Chemical class 0.000 claims description 2
- 238000013461 design Methods 0.000 abstract description 13
- 229910052493 LiFePO4 Inorganic materials 0.000 abstract description 2
- 239000000758 substrate Substances 0.000 abstract 3
- 239000006183 anode active material Substances 0.000 abstract 1
- 238000007599 discharging Methods 0.000 description 13
- 238000002474 experimental method Methods 0.000 description 8
- 239000011247 coating layer Substances 0.000 description 7
- 238000005259 measurement Methods 0.000 description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-methyl-pyrrolidinone Natural products CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 3
- 239000002033 PVDF binder Substances 0.000 description 3
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 3
- 240000007817 Olea europaea Species 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 238000007600 charging Methods 0.000 description 2
- 238000010281 constant-current constant-voltage charging Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- 229910013872 LiPF Inorganic materials 0.000 description 1
- 101150058243 Lipf gene Proteins 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 239000005030 aluminium foil Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 1
- 238000013401 experimental design Methods 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 239000011325 microbead Substances 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Images
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Battery Electrode And Active Subsutance (AREA)
- Secondary Cells (AREA)
Abstract
The invention relates to a LiFePO using low conductivity4A lithium ion secondary battery having a large current discharge capacity as a main component of a positive electrode active material. A lithium ion secondary battery comprises LiFePO4As a main component of the positive electrode active material. In order to make the lithium ion secondary battery have large current discharge capability (the capacity at the discharge rate of 10C is more than 80% of that at the discharge rate of 1C), the lithium ion secondary battery has a lithium ion secondary battery with a high current discharge capabilityThe invention designs the coating containing the anode active material on a current collecting substrate to ensure that the ratio (A/t) of the coating area to the thickness is more than 1.2 multiplied by 106(mm) such that the coating has a reduced ionic resistance; and providing more than one conductive handle on the current collecting substrate of the positive electrode to reduce the electronic impedance of the current collecting substrate, so that the positive electrode has a reduced total impedance. The design of the invention can also be applied to other positive active materials with low conductivity.
Description
Technical field
The invention relates to a kind of lithium rechargeable battery, especially relevant a kind of LiFePO that uses low electrical conductivity with large current discharging capability
4Lithium rechargeable battery as the Main Ingredients and Appearance of positive electrode active materials with large current discharging capability.
Background technology
LiFePO4 (LiFePO
4) have olivine (olive) crystal framework, be one of the positive electrode active materials of the popular lithium rechargeable battery of Recent study.Use LiFePO
4Disadvantage as the positive electrode active materials of lithium rechargeable battery is that its low-down electrical conductivity (is 10
-9The order of magnitude of S/cm), far below positive electrode active materials LiMn commonly used
2O
4Or LiCoO
2The person (10
-3～10
-4S/cm), when causing lithium ion to move into/move out positive pole, meet with obstacle, make and use LiFePO
4Large current discharging capability as the lithium rechargeable battery of positive electrode active materials is affected, than using LiMn
2O
4Or LiCoO
2The person is poor as positive electrode active materials.On the general document in order to solve this LiFePO
4The problem that electrical conductivity is not good all is to set about at preparing raw material, can be divided into following 3 points:
1. criticize and cover carbon-coating at LiFePO
4On the surface, promote its electrical conductivity [1.N.Ravet, J.B.Goodenough, S.Besner, M.Simouneau, P.Hovington and M.Armand, Proceedings of 196
ThECSMeeting, Hawaii, 17～22 October 1999; 2.N.Ravet, Y.Chouinard, J.F.Magnan, S.Besner, M.Gauthier, and M.Armand, J.power sources, 97～98,503 (2001); 3.P.P.Prosini, D.Zane, M.Pasquali, Electrochim.Acta, 46,3517 (2001); 4.H.Huang, S.-C.Yin, F.Nazar, Electrochem.Solid State Lett., 4, A170 (2001); 5.Z.Chen, J.R.Dahn, J.Electrochem.Soc., 149, A1189 (2002)];
2. doping metals is to LiFePO
4Middle its electrical conductivity [1.S.Y.Chung, J.T.Bloking, and Y.M.Chiang, Nat.Mater., 1,123 (2002)] that promotes;
3. use the LiFePO of nanoscale
4, to increase its large current discharging capability [1.A.Yamada, S.C.Chung, and K.Hinokuma, J.Electrochem.Soc., 148, A224 (2001); 2.P.P Prosini, M.Carewska, S.Scaccia, P.Wisniewski, S.Passerini, M.Pasquali, J.Electrochem.Soc., 149,886 (2002); 3.S.Franger, F.Le Cras, C.Bourbon, H.Rouault, Electrochem.Solid State Lett., 5,231 (2002) .].
Present general commercial LiFePO
4Be to cover processing through criticizing of carbon, its granular size is approximately between inferior micron and micro-meter scale; Though LiFePO
4Cover processing via criticizing of carbon, its electrical conductivity can rise to 10
-2To 10
-3Between the S/cm, but large current discharging capability still is very poor, does not also find as yet at present to use the specific electrodes method for designing, solves LiFePO
4The heavy-current discharge problem.
U.S. Patent Publication 2005/0233219A1 and 2005/0233220A1 have disclosed a kind of use LiFePO
4As the lithium rechargeable battery with large current discharging capability of the Main Ingredients and Appearance of positive electrode active materials, wherein this LiFePO
4Further be doped with Ti, Zr, Nb, Al or Mg, and the coating of this positive electrode active materials on a colleeting comb base material has a specific area impedance (area specific impedance; Be called for short ASI) less than 20 Ω-cm
2The content of this two United States Patent (USP) is merged in this case by the reference mode.
Summary of the invention
The present invention discloses a kind of lithium rechargeable battery, comprises LiFePO
4Main Ingredients and Appearance as positive electrode active materials.For make this lithium rechargeable battery have large current discharging capability (the capacitance of 10C discharge rate can greater than 1C discharge rate person 80%), the present invention will be positioned at the coated designs that contains this positive electrode active materials on the colleeting comb base material become its coating area to the ratio (A/t) of its thickness greater than 1.2 x 10
6(mm), make this coating have an ionic resistance that reduces; And conduction handle more than one is set on the colleeting comb base material of positive pole in case of necessity, reduce the electronic impedance of colleeting comb base material, so the total impedance that should positive pole one reduces.Design of the present invention is also applicable to the positive electrode active materials of other low electrical conductivity.
The present invention designs via lithium rechargeable battery, inquires into the influence to the battery discharge ability of the electronic impedance of coating material on positive plate and the positive plate and ionic resistance respectively, to overcome present LiFePO
4Because of the electrical conductivity difference cause can't large current discharging capability shortcoming, prepare lithium rechargeable battery with large current discharging capability, for example greater than 80%, it is adapted at the application of high power products to the 10C discharge rate with respect to the capacitance ratio (hereinafter to be referred as the 10C ability) of 1C discharge rate (hereinafter to be referred as 10C speed).
The preferable concrete enforcement aspect of the present invention includes, but is not limited to following items:
1. a lithium rechargeable battery comprises a positive pole; One negative pole; It separates this positive pole and negative pole one barrier film; And an electrolyte its form a lithium ion passage between this positive pole and the negative pole, wherein this positive pole comprises a colleeting comb (current collector) base material; Be connected the conduction handle (tab) of the single or complex root of this colleeting comb base material; And in the coating of a lip-deep positive electrode of this base material, this positive electrode comprises a positive electrode active materials, conductive carbon and this positive electrode active materials is cohered adhesive (binder) on this base material; Its feature comprises this positive electrode active materials and comprises a Main Ingredients and Appearance LiFePO
4, and its surface area of the coating of this positive electrode to the ratio of its thickness greater than 1.2 x 10
6Mm.
2. as the lithium rechargeable battery of the 1st of project, wherein when this positive pole only comprises single conduction handle, this single conduction handle apart from the maximum distance at this base material edge less than 1200mm; When this positive pole comprises complex root conduction handle, two adjacent conduction handles along the spacing of the length direction of this base material less than 2400mm.
3. as the lithium rechargeable battery of the 1st of project, actual 1KHz impedance (the ACIR)≤30m Ω of the full battery of this battery wherein.
4. as the lithium rechargeable battery of the 2nd of project, wherein the single face coating of this positive electrode has the thickness between 30～150 μ m.
5. as the lithium rechargeable battery of the 2nd of project, wherein this lithium rechargeable battery the capacitance of the discharge rate of 10C at the ratio of the capacitance of the discharge rate of 1C greater than 80%.
6. as the lithium rechargeable battery of the 2nd of project, wherein this positive electrode active materials further comprises LiMn
2O
4, LiCoO
2, Li[Ni, Co, Mn] and O
2, or Li[Ni, Co, Al] O
2
7. a lithium rechargeable battery comprises a positive pole; One negative pole; It separates this positive pole and negative pole one barrier film; And an electrolyte its form a lithium ion passage between this positive pole and the negative pole, wherein this positive pole comprises a colleeting comb (current collector) base material; Be connected the conduction handle (tab) of the single or complex root of this colleeting comb base material; And in the coating of a lip-deep positive electrode of this base material, this positive electrode comprises a positive electrode active materials and this positive electrode active materials is cohered adhesive (binder) on this base material; Its feature comprises this positive electrode active materials and comprises a main component lithium compound, and this lithium compound has 10
-5To 10
-10The electrical conductivity of S/cm magnitude, and its coating area of the coating of this positive electrode to the ratio of its thickness greater than 1.2x 10
6Mm.
8. as the lithium rechargeable battery of the 7th of project, wherein this lithium compound is the lithium transition-metal phosphorus compound.
9. as the lithium rechargeable battery of the 8th of project, wherein this lithium transition-metal phosphorus compound is for having the olivine crystal structure LiMPO of olivine (olive) or modification
4, wherein M is a transition metal.
10. as the lithium rechargeable battery of the 9th of project, this LiMPO wherein
4Be LiFePO
4, metal-doped LiFePO
4, the LiFePO that coats of finishing or carbon
4
11. as the lithium rechargeable battery of the 7th of project, wherein when this positive pole only comprises single conduction handle, this single conduction handle apart from the maximum distance at this base material edge less than 1200mm; When this positive pole comprises complex root conduction handle, two adjacent conduction handles along the spacing of the length direction of this base material less than 2400mm.
12. as the lithium rechargeable battery of the 7th of project, actual 1KHz impedance (the ACIR)≤30m Ω of the full battery of this battery wherein.
13. as the lithium rechargeable battery of the 11st of project, wherein the coating of this positive electrode has the thickness between 30～150 μ m.
14. as the lithium rechargeable battery of the 11st of project, wherein this lithium rechargeable battery the capacitance of the discharge rate of 10C at the ratio of the capacitance of the discharge rate of 1C greater than 80%.
15. as the lithium rechargeable battery of the 11st of project, wherein this positive electrode active materials further comprises LiMn
2O
4, LiCoO
2, Li[Ni, Co, Mn] and O
2, or Li[Ni, Co, Al] O
2
Execution mode
In battery pole plates design, two parts mainly can be divided in the impedance source: 1. electronic impedance, 2. ionic resistance.For the LiFePO that uses low electrical conductivity
4As the anode plate of main active material, the main source of its impedance comprises the electronic impedance of colleeting comb base material and the ionic resistance of a lip-deep coating thereof.
The electronic impedance R of colleeting comb base material
ElectronCan represent by following formula:
R
electron＝1/σ·L/A
Wherein σ is the electron conduction degree of colleeting comb base material, and L is the length of its conducting path, and A is long-pending for its conductive cross-section.
The ionic resistance R of the coating of positive electrode
IonCan represent by following formula:
R
ion＝1/κ·t/A
Wherein K is the ionic conductance of the coating of positive electrode, and t is its single face coating layer thickness, and A is its coating area.
κ＝κ
0·ε
n
Wherein, κ
0The electrical conductivity of=material, ε=pole plate porosity, the curvature (tortuosity) of n=pole plate hole
For understanding LiFePO
4The performance of the 10C speed under the design of different positive poles, shown in Figure 1A to Fig. 1 J, designed the experiment of 10 groups of different anodal length and conduction handle position, to understand the influence of electrons/ions impedance to the discharge capability of this 10C speed, the length (1L=300mm) of wherein representing anodal colleeting comb base material with L, and the conduction handle is represented with the short column bar, wherein is the positive electrode coating in the zone of surface except the conduction handle of the colleeting comb base material of positive pole and covers.
Following table 1 and table 2 have been listed this 10 groups of Experimental design.
The relevant battery making and the actual 1KHz impedance (ACIR) of full battery and the measurement details of 10C speed will illustrate in following embodiment.
Table 1
| Group | 1 (Figure 1A) | 2 (Figure 1B) | 3 (Fig. 1 C) | 4 (Fig. 1 D) | 5 (Fig. 1 E) |
| Pole plate length (mm) | 300 | 600 | 600 | 600 | 2400 |
| Plate width (mm) | 38 | 38 | 38 | 38 | 38 |
| Single face coating layer thickness (t, μ m) | 49 | 49 | 49 | 49 | 49 |
| Coating area (A)/t (mm) | 2.33E+5 | 4.65E+5 | 4.65E+5 | 4.65E+5 | 1.86E+6 |
| |
1 | 1 | 1 | 2 | 2 |
| Conduction handle position | Other | In | Other | Other | In |
| Unit length (mm) * | 300 | 300 | 600 | 300 | 600 |
| ACIR(m-ohm) ** | 64.62 | 35.71 | 46.86 | 33.52 | 16.53 |
| 1C capacitance (discharging current) | 230.7mAh(270mA) | 454.7mAh(500mA) | 431.1mAh(500mA) | 438.1mAh(500mA) | 1855.1mAh(1950mA) |
| The 10C capacitance | 115.7mAh | 333.3mAh | 314.0mAh | 2999.9mAh | 1764.9mAh |
| The 10C ability | 50.1％ | 73.3％ | 72.8％ | 68.5％ | 95.1％ |
*The conduction handle is apart from 1/2 of the distance of the maximum distance at this base material edge or adjacent two conduction handles.
*ACIR is the actual 1KHz impedance of full battery
By the 2nd, 3,4 group of experiment, control identical base material length, change different conductive mechanisms.Because coating area and single face coating layer thickness are identical, fix so can be considered on the coating ionic resistance, and electronic impedance has different influences because conduction handle position and quantity are different.By the practical impedance ACIR of full battery be respectively 35.71,46.86,33.52m Ω, and the 10C ability is respectively 73.3%, 72.8%, 68.5% result and shows, the electronic impedance difference on the colleeting comb is to the 10C ability and do not make significant difference.
By the 1st, 2,5 group of experiment, the control electronic impedance, promptly unit pole plate length (pole plate from conduction handle length) is identical, and the 5th group because conduction handle quantity (parallel way), so increase unit pole plate length makes three groups electronic impedance unanimity.Because coating area difference, so their ionic resistance thereby difference.By the practical impedance (ACIR) of full battery be respectively 64.62,35.71,16.53m Ω, and the 10C ability is respectively 50.1%, 73.3%, 95.1% result and shows that the ACIR difference that ionic resistance causes has appreciable impact to the 10C ability.
In addition, by 1,3 group of experiment, under identical conduction handle quantity and position, the 3rd group unit pole plate length is the 1st group 2 times, so the 3rd group electronic impedance is inevitable greater than the 1st group, but the 3rd group full battery ACIR46.9m Ω is lower than the 1st group 64.6m Ω, and also 50.1% good than the 1st group of the 3rd group 10C ability 72.8%.
Can find by The above results, influence LiFePO
4Large current discharging capability mainly comes from the ionic resistance on the pole plate.
Table 2
| Group | 6 (Fig. 1 F) | 7 (Fig. 1 G) | 8 (Fig. 1 H) | 9 (Fig. 1 I) | 10 (Fig. 1 J) |
| Pole plate length (mm) | 1200 | 1800 | 2400 | 2800 | 4200 |
| Plate width (mm) | 38 | 38 | 38 | 38 | 77 |
| Single face coating layer thickness (t, μ m) | 49 | 49 | 49 | 49 | 49 |
| Coating area (A)/t (mm) | 9.31E+5 | 1.40E+6 | 1.86E+6 | 2.17E+6 | 6.60E+6 |
| |
1 | 1 | 1 | 2 | 5 |
| Conduction handle position | Other | In | In | In | |
| Unit length (mm) | 1200 | 900 | 1200 | 700 | 420 |
| ACIR(m-ohm) | 48.02 | 23.43 | 25.25 | 14.12 | 5.0 |
| 1C capacitance (mAh) (discharging current, mA) | 1142.6(1100) | 1662.1(1650) | 2240.3(2200) | 2550.1(2600) | 8157 (8200) |
| 10C capacitance (mAh) | 977.5 | 1530.6 | 1933.1 | 2194.7 | 7749 |
| The 10C ability | 85.6％ | 92.1％ | 86.3％ | 86.1％ | 95.0％ |
When unit pole plate length is long, LiFePO
4The factor of discharge capability may transfer the palm that electronic impedance is led to by ionic resistance.For avoiding this kind situation to take place, increase the too high problem of electronic impedance that (electrical conductance path is long) back is caused in pole plate length as can be seen by the 9th group of experiment, can add by number that increases the conduction handle and position and give solution.
Because each group experiment is similar in table 1 and the table 2, be that representative is described in detail in following embodiment only therefore with the 5th group of experiment.
Description of drawings
Figure 1A to Fig. 1 J has shown that the present invention comprises different anodal length and conduction handle position to 10 groups of different designs of positive pole, and wherein L is a unit length.
Fig. 2 has shown ratio and U.S. Patent Publication 2005/0233219A1 and the employed specific area impedance of 2005/0233220A1 (area specific impedance, relation ASI) of coating area (the A)/coating layer thickness (t) of 12 groups of different designs among Figure 1A to Fig. 1 J.
Fig. 3 has shown the relation of 10C ability of a ratio w lithium rechargeable battery of coating area (the A)/coating layer thickness (t) of 10 groups of different designs among Figure 1A to Fig. 1 J.
Fig. 4 has shown the relation of 10C ability of actual 1KHz impedance (ACIR) and lithium rechargeable battery of the full battery of 10 groups of different designs among Figure 1A to Fig. 1 J.
Embodiment
Embodiment: the 5th group
Anodal preparation:
8g polyvinylidene fluoride (PVDF) is dissolved in 150g N-N-methyl-2-2-pyrrolidone N-(N-methyl-2-pyrrolidone; NMP) after, add 7g conductive carbon (Timcal Corporation's Super P 1g and KS6 6g) and 85g LiFePO
4(from Phostech company, this LiFePO
4Have the mean particle size of 5 μ m and be coated with the carbon of its 1.2 percentage by weight), make anode sizing agent after mixing, coat uniformly on two surfaces of aluminium foil base material, dry solvent and the pole plate gross thickness (containing 20 μ m base materials) and the capacitance that roll the tool coated on both sides that obtained of back are respectively 118 μ m and 2.72mAh/cm again
2
The preparation of negative pole:
After 10g PVDF is dissolved in 88.7g NMP, add synthetic graphitized carbon (mesophase microbead synthetic graphitic carbon) (the Osaka Gas Co. of Jie's 88g phase microballoon, Ltd., code name MCMB10-28), make cathode size after mixing, coat uniformly on two surfaces of copper foil base material, dry solvent and the pole plate gross thickness (containing 14 μ m base materials) and the capacitance that roll the tool coated on both sides that obtained of back are respectively 90 μ m and 3.0mAh/cm again
2
The assembling of battery:
Get the positive/negative plate of suitable length, used thickness is that (DSM, 14P01E) as the barrier film between them, the back of reeling adds an amount of 1.1M LiPF to 25 μ m PE materials
6EC/EMC electrolyte, (EC is the abbreviation of ethylene carbonate to form cylindrical battery; EMC is the abbreviation of ethyl methyl carbonate).
The measurement of full battery impedance:
The impedance that the AC impedance measures under 1KHz.
The measurement of 1C capacitance:
Behind the battery full charging (1C CCCV, 3.65V, I-Cut:0.01C), with the 1C current discharge to capacitance that 2.3V was measured.
The measurement of 10C capacitance:
Behind the battery full charging (1C CCCV, 3.65V, I-Cut:0.01C), with the 10C current discharge to capacitance that 2.3V was measured.
Different in order to prove design of the present invention with the design of U.S. Patent Publication 2005/0233219A1 and the employed specific area impedance of 2005/0233220A1 (area specific impedance), tabulate down and 3 list in aforementioned table 1 and the table 2 A/t of each experiment and the value of specific area impedance (ASI), Fig. 2 is the graph of a relation of ASI and A/t.
Table 3
| Group | A/t | Specific area impedance (ASI, Ω-cm 2) |
| 1 | 2.33E+5 | 7.37 |
| 2 | 4.65E+5 | 8.14 |
| 3 | 4.65E+5 | 10.68 |
| 4 | 4.65E+5 | 7.64 |
| 5 | 1.86E+6 | 15.07 |
| 6 | 9.31E+5 | 21.90 |
| 7 | 1.40E+6 | 16.02 |
| 8 | 1.86E+6 | 23.03 |
| 9 | 2.17E+6 | 15.02 |
| 10 | 6.60E+6 | 330.00 |
Table 3 is worked as designing requirement coating area of the present invention (A)/t as can be seen greater than 1.2*10
6The time, the ASI of part battery is greater than 20 Ω-cm
2And A/t is less than 1.2*10
6The time, the specific area impedance that the part battery is also arranged is less than 20 Ω-cm
2As can be seen from Figure 2, A/t value and ASI there is no correlation.In addition, the ASI of the 10th Battery pack for example〉20, but the 10C/1C capacitance has only 2.5% than (10C ability); On the contrary, the ASI of the 5th Battery pack＜20, and the 10C ability is up to 95.1%, so the 10C capacitance and the ASI of battery do not have correlation.
Fig. 3 has shown the 10C ability of lithium rechargeable battery of 1st to 10 group of table 1 in 2 and the relation of coating area (A)/coating layer thickness (t).As can be seen from Figure 3, when designing requirement A/t of the present invention greater than 1.2*10
6The time, the 10C ability of battery can be greater than 80%.
Fig. 4 has shown the 10C ability of lithium rechargeable battery of 1st to 10 group of table 1 in 2 and the relation of ACIR.As can be seen from Figure 4, the discharge capability and the ACIR of the 10C speed of battery have correlation, and as ACIR during less than 30m Ω, the 10C ability of battery can be greater than 80%.。
Claims (15)
1. a lithium rechargeable battery comprises a positive pole; One negative pole; It separates this positive pole and negative pole one barrier film; And-electrolyte its form a lithium ion passage between this positive pole and the negative pole, wherein this positive pole comprises a colleeting comb base material; Be connected the conduction handle of the single or complex root of this colleeting comb base material; And in the coating of a lip-deep positive electrode of this base material, this positive electrode comprises a positive electrode active materials, conductive carbon and this positive electrode active materials is cohered adhesive on this base material; It is characterized in that: this positive electrode active materials comprises a Main Ingredients and Appearance LiFePO
4, and its surface area of the coating of this positive electrode to the ratio of its thickness greater than 1.2 x 10
6Mm.
2. lithium rechargeable battery as claimed in claim 1, wherein when this positive pole only comprises single conduction handle, this single conduction handle apart from the maximum distance at this base material edge less than 1200mm; When this positive pole comprises complex root conduction handle, two adjacent conduction handles along the spacing of the length direction of this base material less than 2400mm.
3. lithium rechargeable battery as claimed in claim 1 or 2, the wherein actual 1KHz impedance≤30m Ω of the full battery of this battery.
4. lithium rechargeable battery as claimed in claim 2, wherein the single face coating of this positive electrode have-between the thickness of 30～150 μ m.
5. lithium rechargeable battery as claimed in claim 2, wherein this lithium rechargeable battery the capacitance of the discharge rate of 10C at the ratio of the capacitance of the discharge rate of 1C greater than 80%.
6. lithium rechargeable battery as claimed in claim 2, wherein this positive electrode active materials further comprises LiMn
2O
4, LiCoO
2, Li[Ni, Co, Mn] and O
2, or Li[Ni, Co, Al] O
2
7. a lithium rechargeable battery comprises a positive pole; One negative pole; It separates this positive pole and negative pole one barrier film; And an electrolyte its form a lithium ion passage between this positive pole and the negative pole, wherein this positive pole comprises a colleeting comb base material; Be connected the conduction handle of the single or complex root of this colleeting comb base material; And in the coating of a lip-deep positive electrode of this base material, this positive electrode comprises a positive electrode active materials and this positive electrode active materials is cohered adhesive on this base material; It is characterized in that: this positive electrode active materials comprises a main component lithium compound, and this lithium compound has 10
-5To 10
-10The electrical conductivity of S/cm magnitude, and its coating area of the coating of this positive electrode to the ratio of its thickness greater than 1.2 x 10
6Mm.
8. lithium rechargeable battery as claimed in claim 7, wherein this lithium compound is the lithium transition-metal phosphorus compound.
9. lithium rechargeable battery as claimed in claim 8, wherein this lithium transition-metal phosphorus compound is the olivine crystal structure LiMPO with olivine or modification
4, wherein M is a transition metal.
10. lithium rechargeable battery as claimed in claim 9, wherein this LiMPO
4Be LiFePO
4, metal-doped LiFePO
4, the LiFePO that coats of finishing or carbon
4
11. lithium rechargeable battery as claimed in claim 7, wherein when this positive pole only comprises single conduction handle, this single conduction handle apart from the maximum distance at this base material edge less than 1200mm; When this positive pole comprises complex root conduction handle, two adjacent conduction handles along the spacing of the length direction of this base material less than 2400mm.
12. as claim 7 or 11 described lithium rechargeable batteries, the actual 1KHz impedance≤30m Ω of the full battery of this battery wherein.
13. lithium rechargeable battery as claimed in claim 11, wherein the single face coating of this positive electrode has the thickness between 30～150 μ m.
14. lithium rechargeable battery as claimed in claim 11, wherein this lithium rechargeable battery the capacitance of the discharge rate of 10C at the ratio of the capacitance of the discharge rate of 1C greater than 80%.
15. lithium rechargeable battery as claimed in claim 11, wherein this positive electrode active materials further comprises LiMn
2O
4, LiCoO
2, Li[Ni, Co, Mn] and O
2, or Li[Ni, Co, Al] O
2
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|---|---|---|---|
| CNB2006100026365A CN100502127C (en) | 2006-01-26 | 2006-01-26 | Lithium ion secondary battery with large current discharge capability |
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| CN100502127C true CN100502127C (en) | 2009-06-17 |
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| US12218383B2 (en) * | 2018-04-06 | 2025-02-04 | Panasonic Intellectual Property Management Co., Ltd. | Electrode plate for non-aqueous electrolyte secondary battery, and non-aqueous electrolyte secondary battery |
| JP7078682B2 (en) * | 2019-09-18 | 2022-05-31 | 財團法人工業技術研究院 | Fast charging lithium ion battery |
| EP4228079A4 (en) * | 2021-11-18 | 2024-02-21 | Contemporary Amperex Technology Co., Limited | Battery pack and electric device therefor |
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|---|---|---|---|---|
| CN1348231A (en) * | 2000-10-05 | 2002-05-08 | 索尼株式会社 | Nonaqueous electrolyte battery and solid electrolyte battery |
| CN1349266A (en) * | 2000-10-06 | 2002-05-15 | 索尼株式会社 | Non-aqueous electrolyte secondary cell |
| CN1406401A (en) * | 2000-12-28 | 2003-03-26 | 松下电器产业株式会社 | Nonaqueous electrolytic secondary battery |
| CN1641912A (en) * | 2004-01-02 | 2005-07-20 | 深圳华粤宝电池有限公司 | Lithium ion cell anode, lithium cell using same and its manufacturing method |
| US20050233219A1 (en) * | 2004-02-06 | 2005-10-20 | Gozdz Antoni S | Lithium secondary cell with high charge and discharge rate capability |
-
2006
- 2006-01-26 CN CNB2006100026365A patent/CN100502127C/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1348231A (en) * | 2000-10-05 | 2002-05-08 | 索尼株式会社 | Nonaqueous electrolyte battery and solid electrolyte battery |
| CN1349266A (en) * | 2000-10-06 | 2002-05-15 | 索尼株式会社 | Non-aqueous electrolyte secondary cell |
| CN1406401A (en) * | 2000-12-28 | 2003-03-26 | 松下电器产业株式会社 | Nonaqueous electrolytic secondary battery |
| CN1641912A (en) * | 2004-01-02 | 2005-07-20 | 深圳华粤宝电池有限公司 | Lithium ion cell anode, lithium cell using same and its manufacturing method |
| US20050233219A1 (en) * | 2004-02-06 | 2005-10-20 | Gozdz Antoni S | Lithium secondary cell with high charge and discharge rate capability |
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Effective date of registration: 20200526 Address after: Kaohsiung City, Taiwan, China Patentee after: LONGHUA TECHNOLOGY Corp. Address before: Taiwan County, Hsinchu, China Town, the eastern part of Zhongxing Road, No. four, No. 195 Patentee before: Industrial Technology Research Institute |